US8466460B2 - Fused bithiophene-vinylene polymers - Google Patents

Fused bithiophene-vinylene polymers Download PDF

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US8466460B2
US8466460B2 US13/376,296 US201013376296A US8466460B2 US 8466460 B2 US8466460 B2 US 8466460B2 US 201013376296 A US201013376296 A US 201013376296A US 8466460 B2 US8466460 B2 US 8466460B2
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aryl
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Ashok Kumar Mishra
Subramanian Vaidyanathan
Hiroyoshi Noguchi
Florian Doetz
Silke Annika Koehler
Marcel Kastler
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Flexterra Inc
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Polyera Corp
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Definitions

  • the present invention concerns fused bithophene-vinylene polymers, a thin film semiconductor, as well as electronic, optical and optoelectronic devices containing the polymers.
  • the simplest and most common OFET device configuration is that of a thin-film transistor (TFT), in which a thin film of the organic semiconductor is deposited on top of a dielectric with an underlying gate (G) electrode.
  • TFT thin-film transistor
  • D-S drain-source
  • the current between the S and D electrodes is low when no voltage (V g ) is applied between the G and D electrodes, and the device is in the so called “off” state.
  • V g no voltage
  • I d current (I d ) flows in the channel between the S and D electrodes when a source-drain bias (V d ) is applied, thus providing the “on” state of a transistor.
  • Key parameters in characterizing FET performance are the field-effect mobility ( ⁇ ), which quantifies the average charge carrier drift velocity per unit electric field, and the current on/off ratio (I on :I off ), which is the D-S current ratio between the “on” and “off” states.
  • ⁇ the field-effect mobility
  • I on :I off current on/off ratio
  • the field-effect mobility and on/off ratio should both be as high as possible, for example, having at least ⁇ ⁇ 0.1-1 cm 2 V ⁇ 1 s ⁇ 1 and I on /I off ⁇ 10 6 .
  • the organic semiconductors should satisfy stringent criteria relating to both the injection and current-carrying capacity; in particular: (i) the HOMO/LUMO energies of the material should be appropriate for hole/electron injection at practical voltages; (ii) the crystal structure of the material should provide sufficient overlap of the frontier orbitals (e.g., ⁇ -stacking and edge-to-face contacts) to allow charges to migrate among neighboring molecules; (iii) the compound should be very pure as impurities can hinder the mobility of charge carriers; (iv) the conjugated core of the material should be preferentially oriented to allow charge transport in the plane of the TFT substrate (the most efficient charge transport occurs along the direction of intermolecular ⁇ - ⁇ stacking); and (v) the domains of the crystalline semiconductor should uniformly
  • polymeric organic semiconductors In order to take full advantage of the cost effciencies of solution processing methods such as spin coating, stamping, ink-jet printing or mass printing such as gravure and offset printing, polymeric organic semiconductors would seem to be the material of choice.
  • polythiophenes soluble regioregular polythiophenes such as poly(3-hexylthiophenes) (P3HT), or poly(3,3′′′-didodecylquaterthiophene), poly(2,5-bis-(3-dodecylthiophen-2-yl)-thieno-(3,2-b)thiophene, poly(4,8-didodecyl-2,6-bis-(3-methylthiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene) and their variants are most promising for OTFT applications due to their high charge carrier mobilities.
  • the semiconducting material in solar cell should absorb a significant fraction of the sun's light.
  • Most of the organic semiconducting materials have fairly large band gaps and the absorption bandwidth of these materials is too narrow to absorb a large fraction of the solar spectrum. It is desirable to have a semiconducting material which absorbs further into the visible red and near IR region of the electromagnetic spectrum and has a broad absorption bandwidth.
  • PPVs poly(paraphenylenevinylene)s
  • OLEDs organic light emitting diodes
  • PPVs poly(paraphenylenevinylene)s
  • OLEDs organic light emitting diodes
  • U.S. Pat. No. 6,645,401 discloses conjugated polymers comprising one dithienothiophene recurring unit and a vinylene or acetylene recurring unit, wherein the dithienothiophene is substituted by one or two halogen, aryl, heteroaryl, or straight chain, branched or cyclic alkyl groups, and the vinylene group is unsubstituted or substituted by one or two groups selected from F, Cl an CN.
  • the polymers are said to be useful as optical, electronic and semiconductor materials, in particular as charge transport materials in field effect transistors, as photovoltaics or sensor materials.
  • the present invention provides polymers having semiconducting activity and semiconductor materials prepared from these polymer.
  • the polymers of the present invention contain repeating units A and optionally repeating units B:
  • W is at each occurrence independently a monocyclic or polycylic moiety optionally substituted with 1-4 R a groups;
  • R, R 1 , R 2 , R 5 , R 6 at each occurrence, are independently H, CN, a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 1-30 haloalkyl group, -L-Ar 1 , -L-Ar 1 -Ar 1 , -L-Ar 1 —R 7 , or -L-Ar 1 —Ar 1 —R 7 ;
  • R 3 , R 4 at each occurrence, are independently H, CN, a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 1-30 haloalkyl group, or -L-R 9 ;
  • c is from 1 to 6.
  • Z in unit A is S.
  • X in unit A is N(R 5 ) or Si(R 5 R 6 ).
  • Z in unit A is S and X is N(R 5 ) or Si(R 5 R 6 ).
  • R 5 and R 6 are a C 1-30 alkyl or a C 2-30 alkenyl group.
  • R 1 , R 2 , R 3 and R 4 are hydrogen.
  • R, R 1 , R 2 , R 5 , R 6 are independently H, CN, a C 1-30 alkyl group, a C 2-30 alkenyl group, or a C 1-30 haloalkyl group.
  • R 3 , R 4 are independently H, CN, a C 1-30 alkyl group, a C 2-30 alkenyl group, or a C 1-30 haloalkyl group.
  • R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H, CN, a C 1-30 alkyl group, a C 2-30 alkenyl group, and a C 1-30 haloalkyl group.
  • R 5 and R 6 are a C 1-30 alkyl or C 1-30 haloalkyl or a C 2-30 alkenyl group. In some other preferred embodiments, R 1 , R 2 , R 3 and R 4 are hydrogen. In some specific embodiments, R 5 and R 6 are a C 1-30 alkyl or C 1-30 haloalkyl or a C 2-30 alkenyl group, and R 1 , R 2 , R 3 and R 4 are hydrogen.
  • Z in unit A is S.
  • X in unit A is N(R 5 ) or Si(R 5 R 6 ).
  • Z in unit A is S and X is N(R 5 ) or Si(R 5 R 6 ).
  • Z in unit A is S
  • X is N(R 5 ) or Si(R 5 R 6 )
  • R 5 and R 6 are a C 1-30 alkyl, a C 1-30 haloalkyl or a C 2-30 alkenyl group
  • R 1 , R 2 , R 3 and R 4 are hydrogen.
  • the polymer of the present invention is a homopolymer containing A units. In some embodiments, the polymer of the present invention is a copolymer containing A and B units.
  • the A and B units can be present in random order (random copolymers) or in alternating order (alternating copolymers). In case of random copolymers, the molar ratio of A:B is in general from 0.2:0.8 to 0.8:0.2, preferably from 0.3:0.7 to 0.7:0.3.
  • the average number n of the monomer units A or comonomer units A and B is in general from 2 to 5000. Preferably, n is from 18 to 5000.
  • the polymer of the invention is a homopolymer or an alternating copolymer of the general formula (I)
  • n is an integer greater than 1.
  • the polymers of the present invention can be referred to herein as either polymers or copolymers. Further, the polymers can be embedded with other components for utilization in other semiconductor-based devices.
  • the polymers of the present invention can be used to prepare either p-type or n-type semiconductor materials, which in turn can be used to fabricate various organic electronic articles, structures and devices, including field-effect transistors, unipolar circuitries, complementary circuitries, photovoltaic devices, and light emitting devices.
  • the polymers of the present invention can exhibit semiconductor behavior such as high carrier mobility and/or good current modulation characteristics in a field-effect device, and light absorption/charge separation in a photovoltaic device.
  • semiconductor behavior such as high carrier mobility and/or good current modulation characteristics in a field-effect device, and light absorption/charge separation in a photovoltaic device.
  • other organic semiconductor based devices such as OPVs, OLETs, and OLEDs can be fabricated efficiently using the polymeric materials described herein.
  • the present polymers can possess certain processing advantages such as solution-processability high mobility and/or a wide absorption spectrum.
  • the present invention also provide methods of preparing such polymers and semiconductor materials, as well as various compositions, composites, and devices that incorporate the polymers and semiconductor materials disclosed herein.
  • FIG. 1 shows the UV-Vis spectrum of poly(dithienosilole-vinylene) P3, poly(dithienopyrrole) P4, and—for comparison—poly(bithiophene-vinylene) P5 as dilute solutions.
  • Absorbance (ordinate) is plotted versus wavelength in nm (abscissa).
  • FIG. 2 illustrates four different configurations of thin film transistors: a) bottom-gate top contact, b) bottom-gate bottom-contact, c) top-gate bottom-contact, and d) top-gate top contact; each of which can be used to incorporate polymers of the present teachings.
  • FIG. 3 shows the transistor structure used in Example 2F comprising a gate contact 1 , a dielectric layer 2 , a polymeric semiconductor layer 3 , a substrate 4 , a drain contact 5 and a source contact 6 .
  • FIG. 4 shows the transistor structure used in Examples 2A-2E comprising a gate contact 1 , a dielectric layer 2 , a polymeric semiconductor layer 3 , a drain contact 5 and a source contact 6 .
  • FIG. 5 shows an exemplary transfer plot for poply(dithienosilole-vinylene) based transistors having bottom gates bottom contact (BGBC) architecture, where the active layer was annealed at 200° C.
  • Source Drain Current in Amps (ordinate) is plotted versus Gate Voltage in V (abscissa).
  • FIG. 6 shows an exemplary transfer plot for poly(dithienopyrrole-vinylene) based transistors having bottom gates bottom contact (BGBC), where the active layer was annealed at 125° C.
  • Source Drain Current in Amps (ordinate) is plotted versus Gate Voltage in V (abscissa).
  • FIG. 7 shows an exemplary transfer plot for poly(dithienosilole-vinylene) based transistor having top gate bottom contact (TGBC) architecture, where the active layer was annealed at 230° C.
  • Source Drain Current in Amps (ordinate) is plotted versus Gate Voltage in V (abscissa).
  • Table 1 summarizes the structure, the material for the different components, and the method of fabrication of various exemplary TFTs incorporating representative polymers of the present teachings.
  • the present invention relates to semiconductor materials prepared from fused bithiophene-vinylene polymers.
  • the present invention further relates to methods for preparing these copolymers and semiconductor materials, as well as to compositions, composites, materials, articles, structures, and devices that incorporate such copolymers and semiconductor materials.
  • compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings also consist essentially of, or consist of, the recited components, and that the processes of the present teachings also consist essentially of, or consist of, the recited processing steps.
  • a “p-type semiconductor material” or “p-type semiconductor” refers to a semiconducting material, for example, an organic semiconducting material, having holes as the majority current carriers.
  • a p-type semiconductor when deposited on a substrate, can provide a hole mobility in excess of about 10 ⁇ 5 cm 2 /Vs.
  • a p-type semiconductor material also should exhibit a current on/off ratio of greater than about 1000.
  • n-type semiconductor material or “n-type semiconductor” refers to a semiconducting material, for example, an organic semiconducting material, having electrons as the majority current carriers.
  • an n-type semiconductor when deposited on a substrate, can provide an electron mobility in excess of about 10 ⁇ 5 cm 2 /Vs.
  • a n-type semiconductor material also should exhibit a current on/off ratio of greater than about 1000.
  • solution-processable refers to compounds, materials, or compositions that can be used in various solution-phase processes including spin-coating, printing (e.g., inkjet printing, gravure printing, offset printing), spray coating, electrospray coating, drop casting, dip coating, and blade coating.
  • a “fused ring” or a “fused ring moiety” refers to a polycyclic ring system having at least two rings wherein at least one of the rings is aromatic and such aromatic ring (carbocyclic or heterocyclic) has a bond in common with at least one other ring that can be aromatic or non-aromatic, and carbocyclic or heterocyclic.
  • a “cyclic moiety” can include one or more (e.g., 1-6) carbocyclic or heterocyclic rings.
  • the polycyclic system can include one or more rings fused to each other (i.e., sharing a common bond) and/or connected to each other via a spiro atom.
  • the cyclic moiety can be a cycloalkyl group, a heterocycloalkyl group, an aryl group, or a heteroaryl group, and can be optionally substituted as described herein.
  • halo or “halogen” refers to fluoro, chloro, bromo, and iodo.
  • alkyl refers to a straight-chain or branched saturated hydrocarbon group.
  • alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl groups (e.g., n-pentyl, isopentyl, neopentyl), and the like.
  • an alkyl group can have 1 to 20 carbon atoms, i.e., a C 1-20 alkyl group.
  • an alkyl group can have 1 to 6 carbon atoms, and can be referred to as a “lower alkyl group.”
  • lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and isopropyl), and butyl groups (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl).
  • alkyl groups can be substituted as disclosed herein.
  • An alkyl group is generally not substituted with another alkyl group or an alkenyl or alkynyl group.
  • haloalkyl refers to an alkyl group having one or more halogen substituents.
  • haloalkyl groups include CF 3 , C 2 F 5 , CHF 2 , CH 2 F, CCl 3 , CHCl 2 , CH 2 Cl, C 2 Cl 5 , and the like.
  • Perhaloalkyl groups i.e., alkyl groups wherein all of the hydrogen atoms are replaced with halogen atoms (e.g., CF 3 and C 2 F 5 ), are included within the definition of “haloalkyl.”
  • a C 1-20 haloalkyl group can have the formula —C m X 2t — or —C m H 2m-t X t —, wherein X is F, Cl, Br, or I, m is an integer in the range of 1 to 20, and t is an integer in the range of 0 to 40, provided that m is less than or equal to 2t.
  • Haloalkyl groups that are not perhaloalkyl groups can be optionally substituted as disclosed herein.
  • arylalkyl refers to an -alkyl-aryl group, wherein the arylalkyl group is covalently linked to the defined chemical structure via the alkyl group.
  • An arylalkyl group is within the definition of an —Y—C 6-14 aryl group, where Y is as defined herein.
  • An example of an arylalkyl group is a benzyl group (—CH 2 —C 6 H 5 ).
  • An arylalkyl group can be optionally substituted, i.e., the aryl group and/or the alkyl group can be substituted as disclosed herein.
  • alkenyl refers to a straight-chain or branched alkyl group having one or more carbon-carbon double bonds.
  • alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl groups, and the like.
  • the one or more carbon-carbon double bonds can be internal (such as in 2-butene) or terminal (such as in 1-butene).
  • an alkenyl group can have 2 to 20 carbon atoms, i.e., a C 2-20 alkenyl group.
  • alkenyl groups can be substituted as disclosed herein.
  • An alkenyl group is generally not substituted with another alkenyl group or an alkyl or alkynyl group.
  • alkynyl refers to a straight-chain or branched alkyl group having one or more triple carbon-carbon bonds.
  • alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, and the like.
  • the one or more triple carbon-carbon bonds can be internal (such as in 2-butyne) or terminal (such as in 1-butyne).
  • an alkynyl group can have 2 to 20 carbon atoms, i.e., a C 2-20 alkynyl group.
  • alkynyl groups can be substituted as disclosed herein.
  • An alkynyl group is generally not substituted with another alkynyl group or an alkyl or alkenyl group.
  • cycloalkyl refers to a non-aromatic carbocyclic group including cyclized alkyl, alkenyl, and alkynyl groups.
  • a cycloalkyl group can be monocyclic (e.g., cyclohexyl) or polycyclic (e.g., containing fused, bridged, and/or spiro ring systems), wherein the carbon atoms are located inside or outside of the ring system. Any suitable ring position of the cycloalkyl group can be covalently linked to the defined chemical structure.
  • cycloalkyl groups include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcaryl, adamantyl, and spiro[4.5]decanyl groups, as well as their homologs, isomers, and the like.
  • cycloalkyl groups can be substituted as disclosed herein.
  • heteroatom refers to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, silicon, sulfur, phosphorus, and selenium.
  • cycloheteroalkyl refers to a non-aromatic cycloalkyl group that contains at least one ring heteroatom selected from O, N and S, and optionally contains one or more double or triple bonds.
  • One or more N or S atoms in a cycloheteroalkyl ring can be oxidized (e.g., morpholine N-oxide, thiomorpholine S-oxide, thiomorpholine S,S-dioxide).
  • nitrogen atoms of cycloheteroalkyl groups can bear a substituent, for example, a hydrogen atom, an alkyl group, or other substituents as described herein.
  • Cycloheteroalkyl groups can also contain one or more oxo groups, such as piperidone, oxazolidinone, pyrimidine-2,4(1H,3H)-dione, pyridin-2(1H)-one, and the like.
  • oxo groups such as piperidone, oxazolidinone, pyrimidine-2,4(1H,3H)-dione, pyridin-2(1H)-one, and the like.
  • Examples of cycloheteroalkyl groups include, among others, morpholine, thiomorpholine, pyran, imidazolidine, imidazoline, oxazolidine, pyrazolidine, pyrazoline, pyrrolidine, pyrroline, tetrahydrofuran, tetrahydrothiophene, piperidine, piperazine, and the like.
  • cycloheteroalkyl groups can be substituted as disclosed herein.
  • aryl refers to an aromatic monocyclic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are fused (i.e., having a bond in common with) together or at least one aromatic monocyclic hydrocarbon ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings.
  • An aryl group can have from 6 to 30 carbon atoms in its ring system, which can include multiple fused rings.
  • a polycyclic aryl group can have from 8 to 14 carbon atoms. Any suitable ring position of the aryl group can be covalently linked to the defined chemical structure.
  • aryl groups having only aromatic carbocyclic ring(s) include phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic), and like groups.
  • polycyclic ring systems in which at least one aromatic carbocyclic ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings include, among others, benzo derivatives of cyclopentane (i.e., an indanyl group, which is a 5,6-bicyclic cycloalkyl/aromatic ring system), cyclohexane (i.e., a tetrahydronaphthyl group, which is a 6,6-bicyclic cycloalkyl/aromatic ring system), imidazoline (i.e., a benzimidazolinyl group, which is a 5,6-bicyclic cycloheteroalkyl/aromatic ring system), and pyran (i.e., a chromenyl group, which is a 6,6-bicyclic cycloheteroalkyl/aromatic ring system).
  • aryl groups include benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups, and the like.
  • aryl groups can be substituted as disclosed herein.
  • an aryl group can have one or more halogen substituents, and can be referred to as a “haloaryl” group.
  • Perhaloaryl groups i.e., aryl groups wherein all of the hydrogen atoms are replaced with halogen atoms (e.g., —C 6 F 5 ), are included within the definition of “haloaryl.”
  • an aryl group is substituted with another aryl group and can be referred to as a biaryl group.
  • Each of the aryl groups in the biaryl group can be substituted as disclosed herein.
  • heteroaryl refers to an aromatic monocyclic ring system containing at least 1 ring heteroatom selected from oxygen (O), nitrogen (N), sulfur (S), selenium (Se) and arsenic (As) or a polycyclic ring system where at least one of the rings present in the ring system is aromatic and contains at least 1 ring heteroatom.
  • Polycyclic heteroaryl groups include two or more heteroaryl rings fused together and monocyclic heteroaryl rings fused to one or more aromatic carbocyclic rings, non-aromatic carbocyclic rings, and/or non-aromatic cycloheteroalkyl rings.
  • a heteroaryl group as a whole, can have, for example, from 5 to 14 ring atoms and contain 1-5 ring heteroatoms.
  • the heteroaryl group can be attached to the defined chemical structure at any heteroatom or carbon atom that results in a stable structure.
  • heteroaryl rings do not contain O—O, S—S, or S—O bonds.
  • one or more N or S atoms in a heteroaryl group can be oxidized (e.g., pyridine N-oxide, thiophene S-oxide, thiophene S,S-dioxide).
  • heteroaryl groups include, for example, the 5-membered monocyclic and 5-6 bicyclic ring systems shown below:
  • T is O, S, NH, N-alkyl, N-aryl, or N-(arylalkyl) (e.g., N-benzyl).
  • heteroaryl rings include pyrrolyl, furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuryl, benzothienyl, quinolyl, 2-methylquinolyl, isoquinolyl, quinoxalyl, quinazolyl, benzotriazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisox
  • heteroaryl groups include 4,5,6,7-tetrahydroindolyl, tetrahydroquinolinyl, benzothienopyridinyl, benzofuropyridinyl groups, and the like.
  • heteroaryl groups can be substituted as disclosed herein.
  • solubilizing group refers to a functional group that makes the resultant molecule more soluble in most common organic solvents than a hydrogen atom would if it occupied the same position in a molecule (for the same molecule-solvent combinations).
  • solubilizing groups include, but are not limited to alkyl (eg.
  • alkoxy eg., methyl, ethyl, i-propyl, n-propyl, i-butyl, s-butyl, n-butyl, hexyl, 2-methyl hexyl, octyl, 3,7-dimethyl octyl, decyl, dodecyl, tetradecyl, hexadecyl), alkoxy (eg.
  • an “electron-withdrawing group” (“EWG”) or an “electron-accepting group” or an “electronacceptor” refers to a functional group that draws electrons to itself more than a hydrogen atom would if it occupied the same position in a molecule.
  • electron withdrawing groups include, but are not limited to, halogen or halo (e.g., F, Cl, Br, I), —NO 2 , —CN, —NC, —S(R 0 ) 2 + , —N(R 0 ) 3 + , —SO 3 H, —SO 2 R 0 , —SO 3 R 0 , —SO 2 NHR 0 , —SO 2 N(R 0 ) 2 , —COOH, —COR 0 , —COOR 0 , —CONHR 0 , —CON(R 0 ) 2 , C 1-40 haloalkyl groups, C 6-14 aryl groups, and 5-14 membered electron-poor heteroaryl groups; where R 0 is a C 1-20 alkyl group, a C 2-20 alkenyl group, a C 2-20 alkynyl group, a C 1-20 haloalkyl group, a C 1-20 alky
  • each of the C 1-20 alkyl group, the C 2-20 alkenyl group, the C 2-20 alkynyl group, the C 1-20 haloalkyl group, the C 1-20 alkoxy group, the C 6-14 aryl group, the C 3-14 cycloalkyl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group can be optionally substituted with 1-5 small electronwithdrawing groups such as F, Cl, Br, —NO 2 , —CN, —NC, —S(R 0 ) 2 + , —N(R 0 ) 3 + , —SO 3 H, —SO 2 R 0 , —SO 3 R 0 , —SO 2 NHR 0 , —SO 2 N(R 0 ) 2 , —COOH, —COR 0 , —COOR 0 , —CONHR 0 ,—CON(R 0 ) 2
  • an “electron-donating group” can be used synonymously herein with “electron donor”.
  • an “electron-donating group” or an “electron-donor” refers to a functional group that donates electrons to a neighboring atom more than a hydrogen atom would if it occupied the same position in a molecule.
  • electron-donating groups include —OH, —OR 0 , —NH 2 , —NHR 0 , —N(R 0 ) 2 , and 5-14 membered electron-rich heteroaryl groups, where R 0 is a C 1-20 alkyl group, a C 2-20 alkenyl group, a C 2-20 alkynyl group, a C 6-14 aryl group, or a C 3-14 cycloalkyl group.
  • Various unsubstituted heteroaryl groups can be described as electron-rich (or ⁇ -excessive) or electron-poor (or ⁇ -deficient). Such classification is based on the average electron density on each ring atom as compared to that of a carbon atom in benzene.
  • electron-rich systems include 5-membered heteroaryl groups having one heteroatom such as furan, pyrrole, and thiophene; and their benzofused counterparts such as benzofuran, benzopyrrole, and benzothiophene.
  • Examples of electron-poor systems include 6-membered heteroaryl groups having one or more heteroatoms such as pyridine, pyrazine, pyridazine, and pyrimidine; as well as their benzofused counterparts such as quinoline, isoquinoline, quinoxaline, cinnoline, phthalazine, naphthyridine, quinazoline, phenanthridine, acridine, and purine.
  • Mixed heteroaromatic rings can belong to either class depending on the type, number, and position of the one or more heteroatom(s) in the ring. See Katritzky, A. R and Lagowski, J. M., Heterocyclic Chemistry (John Wiley & Sons, New York, 1960).
  • “semicrystalline polymer” refers to a polymer that has an inherent tendency to crystallize at least partially either when cooled from the melt or deposited from solution, when subjected to kinetically favorable conditions such as slow cooling, or low solvent evaporation rate etc.
  • the crystallization or lack thereof can be readily identified by an expert in the field-of-art by using several analytical methods, for eg. differential scanning calorimetry (DSC) and/or X-ray diffraction (XRD).
  • annealing refers to a post-deposition heat treatment in to the semicrystalline polymer film in ambient or under reduced/increased pressure for a time duration of more than 100 seconds
  • annealing temperature refers to the maximum temperature that the polymer film is exposed to for at least 60 seconds during this process of annealing.
  • DSC differential scanning calorimetry
  • XRD X-ray diffraction
  • alkyl chains can be substituted symmetrically on one or both positions of the thiophene rings and/or on the vinyl linkage.
  • R 1 , R 2 , R 3 and R 4 can independently be a linear or branched C 1-20 alkyl group or a linear or branched C 2-20 alkenyl group.
  • R 1 , R 2 , R 3 , R 4 at each occurrence independently can be selected from n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl and n-hexadecyl.
  • at least one of R 1 and R 2 are H.
  • W is independently a planar and highly conjugated cyclic core, wherein the ring atoms are covalently bonded with alternating single and double bonds.
  • the highly conjugated and planar nature of such cores can promote ⁇ -electron delocalization (thereby increasing stability and lowering LUMO energy), and provide good intermolecular ⁇ -stacking.
  • Suitable cyclic cores include benzene, naphthalene, anthracene, tetracene, pentacene, perylene, pyrene, coronene, fluorene, indacene, indenofluorene, and tetraphenylene, as well as their analogs in which one or more carbon atoms are replaced with a heteroatom such as O, S, Si, Se, N or P.
  • W is an optionally substituted monocyclic, bicyclic or heterocyclic moiety selected from
  • W is a monocyclic, bicyclic or heterocyclic moiety including one or more thienyl, thiazolyl, or phenyl groups, where each of these groups can be optionally substituted as disclosed herein.
  • W can be selected from
  • R 1 , R 2 , R 5 and R 6 are at each occurrence independently from each other and as defined herein.
  • n can be an integer between 2 and 5000. In some embodiments, n can be 18-5000. For example, n can be 8-4000, 8-2000, 8-500, or 8-200. In certain embodiments, n can be 8-100.
  • the polymers of the present invention include repeating units of Formula Ia
  • polymers of the present invention can include repeating units of one or more of Formulae Ib, Ic, Id, Ie, If, Ig, Ih, Ii, Ij, Ik, Il and Im:
  • certain embodiments of the polymers of the present invention can include repeating units of one or more of Formulae Ik, Il, Im, In, Io, Ip, Iq, Ir, Is and It:
  • R 4 , R 5 are independently selected from H, CN, a C 1-30 alkyl group, a C 2-30 alkenyl group, and a C 1-30 haloalkyl group.
  • Copolymers can be prepared in accordance with the procedures outlined in Scheme 1 below:
  • the dialdehyde 2 can be prepared from fused bithiophene compound 1 by treating with n-BuLi in the presence of dimethylformamide.
  • Compound 3 can be synthesized by the well known Wittig reaction between the dialdehyde 2 and the methyltriphenylphosphonium iodide in the presence of n-butyllithium as a base.
  • the copolymer P1 can be synthesized via Heck coupling reaction between the dibromo compound 4 and the divinyl compound 3. Endcapping of the polymer chains can be done by addition of 1-10% monobromo or mono vinyl aromatic or heteroaromatic units before workup of the polymerization mixture is worked up.
  • copolymer P2 can be synthesized following the scheme:
  • polymers of the present invention can be prepared in accordance with the procedures analogous to those described in Schemes 1, 2 and 3.
  • the present polymers can be prepared from commercially available starting materials, compounds known in the literature, or readily prepared intermediates, by employing standard synthetic methods and procedures known to those skilled in the art. Standard synthetic methods and procedures for the preparation of organic molecules and functional group transformations and manipulations can be readily obtained from the relevant scientific literature or from standard textbooks in the field. It will be appreciated that where typical or preferred process conditions (i.e., reaction temperatures, times, mole ratios of reactants, solvents, pressures, etc.) are given, other process conditions can also be used unless otherwise stated.
  • Optimum reaction conditions can vary with the particular reactants or solvent used, but such conditions can be determined by one skilled in the art by routine optimization procedures. Those skilled in the art of organic synthesis will recognize that the nature and order of the synthetic steps presented can be varied for the purpose of optimizing the formation of the compounds described herein.
  • product formation can be monitored by spectroscopic means, such as nuclear magnetic resonance spectroscopy (NMR, e.g., 1 H or 13 C), infrared spectroscopy (IR), spectrophotometry (e.g., UV-visible), mass spectrometry (MS), or by chromatography such as high pressure liquid chromatograpy (HPLC), gas chromatography (GC), gel-permeation chromatography (GPC), or thin layer chromatography (TLC).
  • NMR nuclear magnetic resonance spectroscopy
  • IR infrared spectroscopy
  • spectrophotometry e.g., UV-visible
  • MS mass spectrometry
  • chromatography such as high pressure liquid chromatograpy (HPLC), gas chromatography (GC), gel-permeation chromatography (GPC), or thin layer chromatography (TLC).
  • HPLC high pressure liquid chromatograpy
  • GC gas chromatography
  • GPC gel-permeation chromatography
  • Suitable solvents typically are substantially nonreactive with the reactants, intermediates, and/or products at the temperatures at which the reactions are carried out, i.e., temperatures that can range from the solvent's freezing temperature to the solvent's boiling temperature.
  • a given reaction can be carried out in one solvent or a mixture of more than one solvent.
  • suitable solvents for a particular reaction step can be selected.
  • Exemplary polymers from the present invention include:
  • the molecular weights of the polymers of the present invention can be determined using size exclusion chromatography (SEC).
  • SEC size exclusion chromatography
  • M n molecular weight
  • PDI polydispersity index
  • PDI polydispersity index
  • the polymers of the invention can be used to prepare semiconductor materials (e.g., compositions and composites), which in turn can be used to fabricate various articles of manufacture, structures and devices.
  • semiconductor materials incorporating one or more polymers of the present teachings can exhibit n-type semiconducting activity and in some embodiments, semiconductor materials incorporating one or more polymers of the present teachings can exhibit p-type or ambipolar semiconducting activity.
  • the invention provides for electronic devices, optical devices, and optoelectronic devices comprising one or more polymers of the invention.
  • the invention provides for a thin film semiconductor comprising one or more polymers of the invention and a field effect transistor device comprising the thin film semiconductor.
  • the field effect transistor device has a structure selected from top-gate bottom-contact structure, bottom-gate top-contact structure, top-gate top-contact structure, and bottom-gate bottom-contact structure.
  • the field effect transistor device comprises a dielectric material, wherein the dielectric material comprises an organic dielectric material, an inorganic dielectric material, or a hybrid organic/inorganic dielectric material.
  • the invention provides for photovoltaic devices and organic light emitting devices comprising the thin film semiconductor comprising one or more polymers of the invention.
  • the compounds of the present invention can offer processing advantages when used to fabricate electrical devices such as thin film semiconductors, field-effect devices, organic light emitting diodes (OLEDs), organic photovoltaics, photodetectors, capacitors, and sensors.
  • a compound can be considered soluble in a solvent when at least 0.1 mg of the compound is soluble in 1 mL of the solvent.
  • Examples of common organic solvents include petroleum ethers; acetonitrile; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones, such as acetone, and methyl ethyl ketone; ethers, such as tetrahydrofuran, dioxane, bis(2-methoxyethyl) ether, diethyl ether, diisopropyl ether, and t-butyl methyl ether; alcohols, such as methanol, ethanol, butanol, and isopropyl alcohol; aliphatic hydrocarbons, such as hexanes; acetates, such as methyl acetate, ethyl acetate, methyl formate, ethyl formate, isopropyl acetate, and butyl acetate; halogenated aliphatic and aromatic hydrocarbons, such as dichloromethane, chloroform, ethylene chloride
  • the present invention also provides for compositions comprising one or more polymers of the invention dissolved or dispersed in a liquid medium.
  • the liquid medium comprises water and/or an organic solvent and optionally one or more additives independently selected from viscosity modulators, detergents, dispersants, binding agents, compatibilizing agents, curing agents, initiators, humectants, antifoaming agents, wetting agents, pH modifiers, biocides, and bactereriostats.
  • the present polymers can exhibit versatility in their processing.
  • Formulations including the present polymers can be printable via different types of printing techniques including gravure printing, flexographic printing, and inkjet printing, providing smooth and uniform films that allow, for example, the formation of a pinhole-free dielectric film thereon, and consequently, the fabrication of all-printed devices.
  • the present invention therefore, further provides methods of preparing a semiconductor material.
  • the methods can include preparing a composition that includes one or more polymers disclosed herein dissolved or dispersed in a liquid medium such as a solvent or a mixture of solvents, depositing the composition on a substrate to provide a semiconductor material precursor, and processing (e.g., heating) the semiconductor precursor to provide a semiconductor material (e.g., a thin film semiconductor) that includes a polymer disclosed herein.
  • the depositing step can be carried out by printing, including inkjet printing and various contact printing techniques (e.g., screen-printing, gravure, offset, pad, and microcontact printing).
  • the depositing step can be carried out by vacuum vapor deposition, spin coating, drop-casting, zone casting, dip coating, blade coating, or spraying.
  • the present invention further provides articles of manufacture, for example, composites that include a semiconductor material of the present teachings and a substrate component and/or a dielectric component.
  • the substrate component can be selected from materials including doped silicon, an indium tin oxide (ITO), ITO-coated glass, ITO-coated polyimide or other plastics, aluminum or other metals alone or coated on a polymer or other substrate, a doped polythiophene, and the like.
  • the dielectric component can be prepared from inorganic dielectric materials such as various oxides (e.g., SiO 2 , Al 2 O 3 , HfO 2 ), organic dielectric materials such as various polymeric materials (e.g., the crosslinked polymer blends described in U.S. patent application Ser. Nos.
  • the composite also can include one or more electrical contacts.
  • Suitable materials for the source, drain, and gate electrodes include metals (e.g., Au, Al, Ni, Cu), transparent conducting oxides (e.g., ITO, IZO, ZITO, GZO, GIO, GITO), and conducting polymers (e.g., poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), polyaniline (PANI), polypyrrole (PPy)).
  • metals e.g., Au, Al, Ni, Cu
  • transparent conducting oxides e.g., ITO, IZO, ZITO, GZO, GIO, GITO
  • conducting polymers e.g., poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), polyaniline (PANI), polypyrrole (PPy)).
  • One or more of the composites described herein can be embodied within various organic electronic, optical, and opto-electronic devices such as organic thin film transistors (OTFTs), specifically, organic field effect transistors (OFETs), as well as sensors, solar cells, capacitors, complementary circuits (e.g., inverter circuits), and the like.
  • OFTs organic thin film transistors
  • OFETs organic field effect transistors
  • sensors solar cells
  • capacitors capacitors
  • complementary circuits e.g., inverter circuits
  • an aspect of the present invention relates to methods of fabricating an organic field effect transistor that incorporates a semiconductor material of the present teachings.
  • the semiconductor materials of the present teachings can be used to fabricate various types of organic field effect transistors including top-gate top-contact capacitor structures, top-gate bottom-contact capacitor structures, bottom-gate top-contact capacitor structures, and bottomgate bottom-contact capacitor structures.
  • FIG. 2 illustrates the four common types of OFET structures: (a) bottom-gate top-contact structure, (b) bottom-gate bottom-contact structure, (c) top-gate bottom-contact structure, and (d) top-gate top-contact structure. As shown in FIG.
  • an OFET can include a dielectric layer (e.g., shown as 8 , 8 ′, 8 ′′, and 8 ′′′ in FIGS. 2 a , 2 b , 2 c , and 2 d , respectively), a semiconductor layer (e.g., shown as 6 , 6 ′, 6 ′′, and 6 ′′′ in FIGS. 2 a , 2 b , 2 c , and 2 d , respectively), a gate contact (e.g., shown as 10 , 10 ′, 10 ′′, and 10 ′′′ in FIGS.
  • a dielectric layer e.g., shown as 8 , 8 ′, 8 ′′, and 8 ′′′ in FIGS. 2 a , 2 b , 2 c , and 2 d , respectively
  • a semiconductor layer e.g., shown as 6 , 6 ′, 6 ′′, and 6 ′′′ in FIGS. 2 a , 2 b , 2 c ,
  • a substrate e.g., shown as 12 , 12 ′, 12 ′′, and 12 ′′′ in FIGS. 2 a , 2 b , 2 c , and 2 d , respectively
  • source and drain contacts e.g., shown as 2 , 2 ′, 2 ′′, 2 ′′′, 4 , 4 ′, 4 ′′, and 4 ′′′ in FIGS. 2 a , 2 b , 2 c , and 2 d , respectively.
  • polymers of the present teachings are useful is photovoltaics or solar cells.
  • the polymers of the present teachings can exhibit broad optical absorption. Accordingly, the polymers described herein can be used as an n-type or p-type semiconductor in a photovoltaic design, which includes an adjacent p-type or n-type semiconducting material respectively to form a p-n junction.
  • the polymers can be in the form of a thin film semiconductor, which can be a composite of the thin film semiconductor deposited on a substrate. Exploitation of the polymers of the present teachings in such devices is within the knowledge of the skilled artisan.
  • another aspect of the present invention relates to methods of fabricating an organic field effect transistor that incorporates a semiconductor material of the present teachings.
  • the semiconductor materials of the present invention can be used to fabricate various types of organic field effect transistors including top-gate top-contact capacitor structures, top-gate bottom-contact capacitor structures, bottom-gate top-contact capacitor structures, and bottom-gate bottom-contact capacitor structures.
  • OTFT devices can be fabricated with the present compounds on doped silicon substrates, using SiO 2 as the dielectric, in top-contact geometries.
  • the active semiconducting layer which incorporates at least a compound of the present teachings can be applied by spin-coating or jet printing.
  • metallic contacts can be patterned on top of the films using shadow masks.
  • OTFT devices can be fabricated with the present polymers on plastic foils, using polymers as the dielectric, in top-gate bottom-contact geometries.
  • the active semiconducting layer which incorporates at least a polymer of the present teachings can be deposited at room temperature or at an elevated temperature.
  • the active semiconducting layer which incorporates at least a polymer of the present teachings can be applied by spin-coating or printing as described herein.
  • Gate and source/drain contacts can be made of Au, other metals, or conducting polymers and deposited by vapor-deposition and/or printing.
  • N-bromosuccinimide (1.20 g, 6.76 mmol) was dissolved in DMF (5 mL) and added dropwise at 0° C. to a stirred solution of dithienopyrrole 7 (1.24 g, 3.07 mmol) in DMF (10 mL). Then the reaction mixture was stirred for 1 h at room temperature. The reaction was quenched by addition of ice water. The product was extracted with diethyl ether. The combined organic fractions were washed with brine and dried over sodium sulfate.
  • Compound 6 is commercially available.
  • FIG. 1 shows the UV-Vis spectrum of poly(dithienosilole-vinylene) P3, poly(dithienopyrrole) P4, and poly(bithiophene-vinylene) P5.
  • the UV-Vis. absorption spectra show that, by introducing the bridging group between two thiophenes either with silicon i.e polymer P3 or nitrogen i.e polymer P4, a red shift by about 75 nm in the absorption maximum of the new polymers compared to polymer P5 is observed. In films, this shift is expected to be even more pronounced leading to better harvesting of light for OPV applications due to better overlap with the solar spectrum.
  • 2,7-Dibromo-4,4-dihexadecylcyclopentadithiophene 9 (150 mg, 0.19 mmol), dibromobenzothiadiazole 10 (60 mg, 0.19 mmol), Pd 2 dba 3 (10 mg, 0.03 eq.), and P(o-tolyl) 3 (7 mg, 0.06 eq.) were added to the rbf and degassed for three times. After that, (E)-1,2-bis-(tributylstannyl)ethane 11 (230 mg, 0.38 mmol), and chlorobenzene (19 mL) were added and the mixture was stirred at 130° C. for 48 h.
  • 2,7-Dibromo-4,4-dihexadecylcyclopentadithiophene 9 (200 mg, 0.25 mmol), dibromobenzothiadiazole 10 (30 mg, 0.11 mmol), Pd 2 dba 3 (10 mg, 0.03 eq.), and P(o-tolyl) 3 (7 mg, 0.06 eq.) were added to the rbf and degassed for three times. After that, (E)-1,2-bis-(tributylstannyl)ethane 11 (230 mg, 0.36 mmol), and chlorobenzene (18 mL) were added and the mixture was stirred at 130° C. for 48 h.
  • Top-gate bottom-contact (TGBC) TFTs were fabricated on glass (PGO glass) and were used as received.
  • a 20-60 mg/ml solution of Polystyrene in a proprietary formulation was spincoated (1500-2000 rpm) and the dielectric film was dried at 100° C. for 1 minute. The resulting dielectric thickness is 300-400 nm.
  • a dual-channel Keithley 2612 or a Keithley 4200 semiconductor characterization system with 3 source measurement units (SMUs) configured with preamplifiers was used to perform all electrical characterizations of the fabricated transistors.
  • the other major component of the test system is a Signatone probe station.
  • a dark/metal box enclosure was used to avoid light exposure and to reduce environmental noise.
  • Transistor carrier mobilities were calculated by standard field effect transistor equations. In traditional metal-insulator-semiconductor FETs (MISFETs), there is typically a linear and saturated regime in the I DS vs V DS curves at different V G (where I DS is the source-drain saturation current, V DS is the potential between the source and drain, and V G is the gate voltage).
  • MISFETs metal-insulator-semiconductor FETs
  • the threshold voltage (V t ) can be estimated as the x intercept of the linear section of the plot of V G versus (I DS ) 1/2 .
  • Table 1 summarizes the structure, the material for the different components, and the method of fabrication of the devices made from polymers P3 and P4.
  • photovoltaic devices can be made by blending polymer P3 or P4 with electron acceptors such as 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-C 61 (PCBM) or perylenediimide (PDI) derivatives and casting films from a common solvent onto a bottom substrate that can also act as one of the electrodes.
  • the device is completed by deposition of the counter electrode on top.
  • the ratio of the polymer to the electron acceptor can be carefully optimized by experiment.
  • the film may be optionally annealed to achieve the right morphology.
  • Other electron acceptors can also be used, and other architectures such as dye sensitized solar cell (DSSC) are also possible.
  • DSSC dye sensitized solar cell
  • Table 2 summarizes the structure, the method of fabrication and the results obtained for devices made from polymers P6 and P7.

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US20140142265A1 (en) * 2011-07-05 2014-05-22 Basf Dithienophthalimide semiconductor polymers
US9006725B2 (en) * 2011-07-05 2015-04-14 Basf Se Dithienophthalimide semiconductor polymers

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